Journal of Natural Gas Chemistry 12(2003)219227

Direct Dimethyl Ether Synthesis

Takashi Ogawa ,

Norio Inoue,

Tutomu Shikada,

Yotaro Ohno

DME Development Co., Ltd, Shoro-koku Shiranuka-ch, Hokkaido, 088-0563 Japan

[Manuscript received September 1, 2003; revised October 20, 2003]

Abstract: Dimethyl ether (DME) is a clean and economical alternative fuel which can be produced from
natural gas through synthesis gas. The properties of DME are very similar to those of LP gas. DME can
be used for various fields as a fuel such as power generation, transportation, home heating and cooking,
etc. It contains no sulfur or nitrogen. It is not corrosive to any metal and not harmful to human body. An
innovative process of direct synthesis of DME from synthesis gas has been developed. Newly developed
catalyst in a slurry phase reactor gave a high conversion and high selectivity of DME production. One
and half year pilot scale plant (5 tons per day) testing, which was supported by METI, had successfully
finished with about 400 tons DME production.
Key words: dimethyl ether, DME, slurry reactor, natural gas, syn-gas, coal, clean fuel, diesel engine

1. Introduction
Future energy demand especially in the pacific
and Asian regions is forecasted to be huge. Therefore
limited energy supply as well as environmental issue
caused by consumption of fuel would be substantial
obstacles to realize constant economic growth in these
regions. Dimethyl ether (DME), which is recently recognized as a new clean fuel and is synthesized from
natural gas, will give a solution of secure energy supply and environmental conservation.
DME is a colorless gas at an ambient condition
and easily liquefied under light pressure. Since its
physical and chemical characteristics are very similar
to those of LP gas, it is an easy substitute for LP gas.
Almost half of household in Japan use LP Gas for
cooking and home heating. DME is not only an easy
substitute for LP gas, but also a very clean substitute
for diesel fuel because a DME fueled diesel car emits
neither soot nor particle matters (PM) [1].
DME can be distributed and stored by using LP
gas handling technology, which means DME does not
need costly LNG tankers or LNG terminals [2]. Once

natural gas is converted to DME, it will provide a new

competitive route to transport natural gas compared
with the LNG chain.
DME is now manufactured with two processes,
which are methanol synthesis and methanol dehydration process. In order to use DME as a fuel, it must
be produced at low cost in large quantities. DME
synthesis from synthesis gas (syn-gas: H2 +CO gas)
developed for these years [35]. JFE (formally NKK)
Corporation has been making remarkable progress in
a development of direct DME synthesis from syn-gas
with a bubble column slurry reactor since 1989 [69].
This JFE Direct DME Synthesis will open a new way
to economical DME mass production.
JFE Co., collaborating with Taiheiyo Coal Mining
Co., Sumitomo Metal Industry, Ltd. and CCUJ (Center for Coal Utilization, Japan), finished a project of
5 ton-DME/day (5TPD) pilot plant in 2001 very successfully [10]. This project was funded by Ministry of
Economy, Trade and Industry (METI).
Based on this achievement, DME Development
Co., Ltd started 100 ton-DME/day (100TPD) demoplant project at Hokkaido Japan in 2002.

Corresponding author. Tel: +81-1547-5-9245; Fax: +81-1547-5-9247

E-mail: ogawa@dme-development.com

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2. Whats DME?
DME is the simplest ether having the chemical
formula of CH3 OCH3 . DME is now used almost only
for a spray propellant (paints, agricultural chemicals,
cosmetics, etc.). Approximately 10,000 tons/year
are produced in Japan, and about 150,000 tons/year
worldwide. Table 1 shows physical properties and

combustion characteristics of DME and other relating fuels. DME is a colorless gas at an ambient condition. As its vapor pressure is about 0.6 MPa at
25 , DME is easily liquefied under light pressure.
Its physical properties are similar to those of propane
and butane, which are the principal constituents of
LP gas.

Table 1. Physical properties of DME and other fuel

Properties Chemical Boiling
formula

point
(K)

Liquid
density

Specific

Heat of

Vapor

Ignition

Explosion Cetane

gravity vaporization pressure temperature

(g/cm3 )a (vs. air)

(kJ/kg)

(atm)a

limit

number b

Net

Net

calorific

calorific

value

value

(K)

(106 J/Nm3 ) (106 J/kg)

DME

CH3 OCH3

247.9

0.67

1.59

467

6.1

623

3.417

5560

59.44

Propane

C 3 H8

231

0.49

1.52

426

9.3

777

2.19.4

(5)b

91.25

28.90
46.46

Methane

CH4

111.5

0.55

510

905

515

36.0

50.23

Methanol

CH3 OH

337.6

0.79

1,097

743

5.536

21.10

Diesel

180370

0.84

0.66.5

4055

41.86

a: at 293 K; b: estimated value

Synthesized DME contains neither sulfur nor nitrogen. A toxicity study of DME has confirmed that
its toxicity is very low, similar to LP gas, far much
lower than Methanol. DME does not corrode any
metals. Some artificial rubbers swell in liquid DME,
but, for example, NBR (Nitric rubber) is durable and
can be used in liquid and gas conditions. Since DME
is decomposed in a troposphere in dozens of hours, it
does not cause ozone layer depletion [11].
DMEs calorific value of 28.90 106 J/kg is 1.37
times higher than that of methanol. Its calorific value
of 59.44 106 J/Nm3 as a gas is 1.65 times higher
than that of methane. Although DME has about 65%
of propanes calorific value, a same size of DME tank
can store or carry 85% energy of propane because
DMEs liquid density is 1.37 times heavier than that
of propane.
DME flame is visible blue like that of natural gas.
A cooking oven for natural gas can be used for DME
with very small modification. Cetane number of DME
is very high so that it can be used as diesel substitute,
and DME combustion exhaust gas is far much cleaner
than that of diesel [1].
3. Direct DME synthesis process
3.1. Direct DME synthesis from hydrogen and
carbon monoxide
Table 2 shows reactions concerning with direct

DME synthesis and their reaction heats. There are

mainly two overall reaction routes that synthesize
DME from synthesis gas (syn-gas: H2 +CO gas), reaction (a) and (b). The reaction (a) synthesizes DME
in three steps, which are methanol synthesis reaction
(c), dehydration reaction (d) and water-gas shift reaction (e). When the shift reaction does not take place,
reaction (c) and (d) are combined to the reaction (b),
which is the other DME synthesis route. Haldor Topsoe A/S and some other direct DME syntheses follow
reaction (b) [3]. JFE direct DME synthesis follows
reaction (a).
Table 2. Reaction formulas concerning
DME synthesis
Reaction

Reaction heat
(kJ/mol)

(a)

3CO+3H2 CH3 OCH3 +CO2

-246

(b)

2CO+4H2 CH3 OCH3 +H2 O

-205

(c)

2CO+4H2 2CH3 OH

-182

(d)
(e)

2CH3 OH CH3 OCH3 +H2 O

CO+H2 O CO2 +H2

-23
-41

Since both reaction (a) and (b) generate two

molecules of products from six molecules of syn-gas,
the higher reaction pressure gives higher syn-gas conversion. In consideration of process design, JFE Direct DME Synthesis reaction pressure is around 3 to
7 MPa, and its standard pressure is 5 MPa. Table 3
shows reaction conditions. A catalyst loading ratio,

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Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

W/F, is defined as a ratio of catalyst weight (kg) to

reactant gas flow rate ((kgmol)/h).

Table 3. Reaction conditions of direct DME synthesis

Reaction condition

Pressure/MPa

Fed syn-gas H 2 /CO ratio

W/F/((kgh)/kg)

Experimental

Temperature/
240280

3.07.0

0.52.0

3.08.0

Standard

260

5.0

1.0

4.0

Methanol synthesis is an equilibrium-restricted

reaction. However when the dehydration reaction
(d) takes place simultaneously, the syn-gas conversion rises dramatically. Figure 1 shows stoichiometric
equilibrium syn-gas conversion of DME synthesis (a)
and (b) under 5 MPa, and methanol synthesis (c) under 5 and 9 MPa.

Figure 2. Equilibrium conversion of synthesis gas

vs. H2 /CO ratio

Figure 1. Stoichiometric equilibrium conversion of

DME and methanol synthesis

Compared DME synthesis reaction (a) with reaction (b), reaction (a) gives much higher syn-gas conversion in all temperature conditions.
Figure 2 also shows syn-gas conversions of the two
overall DME syntheses, (a) and (b), and the methanol
synthesis (c), as a function of H2 /CO ratio of syn-gas.
In each reaction, the equilibrium conversion reaches
its maximum point when the H2 /CO ratio is equal to
its stoichiometric number, which are 1.0 for (a) and
2.0 for both (b) and (c). The maximum equilibrium
conversion of (a) is higher than (b) by more than 10
points.

Reaction (a) has some other process advantages

compared with reaction (b). In overall reaction (a),
reaction (e) simultaneously converts by-product water, therefore the water does not accumulate near the
synthesis catalyst. Water leads the catalyst to degradation. To bring longer catalyst life, its important to
avoid water accumulation over time.
By-product of reaction (a) is CO2 . Separation
or distillation of DME from CO2 is much efficient and
not energy consuming compared with separation from
water (in the case of reaction (b)). Because of these
reasons, JFE direct DME synthesis focused the development of the catalyst system and its reaction process
on the reaction (a).
In the process of direct DME synthesis from natural gas, the natural gas will be converted to syn-gas
of H2 /CO=1 at first with O2 and by-product CO2 of
the reaction (a) in an auto-thermal reformer (ATR)
by the following overall reaction (f). Then the total
reaction follows overall reaction (g), and eventually
natural gas (methane) is converted DME and water
via reaction (g), just like via natural gas steam reforming plus DME synthesis reaction (b).

Table 4. DME synthesis from natural gas in the direct DME synthesis plant
Unit
(ATR)
(DME synthesis reactor)
(DME plant total)

Reaction
2CH4 +O2 +CO2 3CO+3H2 +H2 O

(f)

3CO+3H2 CH3 OCH3 (DME)+CO2

(a)

2CH4 +O2 CH3 OCH3 (DME)+H2 O

(g)

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Takashi Ogawa et al./ Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

3.2. A liquid phase slurry reactor

The reaction of DME synthesis is highly exothermic, and catalyst is gradually deactivated at high temperature (over 300 ). Then it is very crucial to remove the reaction heat and to control the reactor temperature even. The direct DME synthesis reactor is
specialized with a liquid phase reactor (DME slurry
reactor) and newly developed catalyst system that realizes the reaction (a) efficiently. Figure 3 shows an
image of the DME slurry reactor.

Figure 3. Concept of slurry reactor for direct DME

synthesis

Catalyst is present as a fine powder slurried in inert high-boiling-point oil. Syn-gas is fed from the bottom of the reactor and forms small and homogeneous
bubbles that react while rising in the catalyst slurry.
Thanks to its homogeneous liquid phase mixing, tem-

perature in the reactor is homogenized so that it is

easily controlled at a high syn-gas conversion (very
exothermic condition). The catalyst was modified to
promote the three reactions (c), (d) and (e) simultaneously in the slurry reactor. There are much fewer
restrictions to the catalyst shape and strength in the
slurry reactor than in a fixed bed reactor.
3.3. JFE direct DME synthesis process
Figure 4 shows a schematic process flow diagram
of the direct DME synthesis process from natural gas.
The process consists of mainly three sections, syn-gas
preparation (auto-thermal reformer), DME synthesis (slurry reactor), and separation/purification (CO2 ,
DME, methanol distillation columns).
Natural gas is converted to syn-gas with O2
(steam) and by-product CO2 in an auto-thermal reformer (ATR). The syn-gas is compressed and fed to
the DME slurry reactor. The effluent from the reactor
is DME, by-product CO2 , small amount of methanol
and unreacted syn-gas. DME and other by-products
are chilled and separated as a liquid from unreacted
gas. In this separation DME works as a solvent to remove CO2 from unreacted syn-gas, which is recycled
to the reactor. DME and other by-products are fed
to the distillation columns. DME and methanol are
purified. CO2 is recycled to the ATR and converted
to syn-gas. Methanol is also recycled to the DME
reactor and finally converted to DME.

Figure 4. Schematic process flow diagram of JFE direct DME synthesis process

4. Process development
4.1. 5TPD project
JFE started the DME synthesis process development with a 50 kg/d bench plant in 1994 [8].
5TPD pilot plant project started in 1997 at Kushirocity in Hokkaido Japan, collaborating with Taiheiyo
Coal Mining Co., Sumitomo Metal Industry LTD and
CCUJ (Center for Coal Utilization, Japan). This

project was funded by METI.

After finishing the construction of the plant, its
operation started in September 1999 and very successfully finished in December 2000. During the one
and half years, six plant operation runs were conducted. Total plant operation time reached 4,300
hours (syn-gas production: about 4,100 h, DME production: about 3,000 h). Total amount of produced
DME was about 400 tons.

Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

4.2. Process flow of 5TPD pilot plant

Figure 5 shows the process flow of 5TPD pilot
plant. Picture 1 shows the plant. Since natural
gas was not available at Kushiro-city (the plant site)

223

during the operation period, LP gas and Coal Bed

Methane were used as feedstock. Basic process flow
of the plant was almost same as those of Figure 4.
The dimensions of the slurry phase reactor were of
0.55 meter-diameter and 15 meter-height.

Figure 5. Process flow of the 5TPD DME pilot plant

Picture 1. The 5TPD DME pilot plant

4.3. Experimental results

(1) Effect of reaction temperature and pressure
The dependence of once-through conversion on
the reaction pressure and temperature is shown in
Figures 6 and 7.
In the Figure 7, by-product CO2 was eliminated

from the selectivity calculation. Figure 6 shows that

the CO conversion increased with pressure, corresponding to the higher equilibrium conversion at the
higher pressure.
The once-through CO conversion reached higher
and 5 MPa. The converthan 50% at 260
sion increased kinematically with temperature but has

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Takashi Ogawa et al./ Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

its maximum because the equilibrium conversion restricts it. Figure 7 shows the DME catalyst did not
synthesize undesirable heavier by-products such as
wax or higher alcohols.

(2) The catalyst life

Continuous experiment for 1,000 h was conducted
to clarify the change of catalyst activity. Sulfur content in the syn-gas was controlled under 1.0106
to avoid poisoning the catalyst. The degradation of
the CO conversion was confirmed to be lower than
10 points of the initial value after 1,000 h operation.
The selectivity was almost constant. This pattern of
degradation of the activity was almost same as that
of conventional methanol synthesis catalyst or fixed
bed DME synthesis catalyst [3]. As a result of the life
test, this catalyst system has commercial durability.

Figure 6. CO conversion vs. reaction conditions

Figure 8.
The catalyst life test
Reaction conditions: 260 , 5 MPa, W/F=4 (gh)/mol, molar
ratio of H2 to CO is 1.0

Figure 7. Product selectivity vs.

tions

reaction condi-

Figure 9. Typical material balance of 5TPD pilot plant

(3) Process material balance

Figure 9 shows a typical example of the material balance of 5TPD pilot plant. Steam and recycled
CO2 were both fed to the ATR to control the reforming reaction and the composition of syn-gas. H2 /CO
ratio of this syn-gas was controlled to 1.04, which was
the best ratio to maximize DME productivity in this
case. DME yield achieved 5.7 tons per day and total
CO conversion reached almost 95% in this material
balance.

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Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

(4) The catalyst activity in terms of W/F

Figure 10 shows once-through CO conversion of
the 50 kg/d bench plant and the 5TPD pilot plant,
as a function of W/F. Once-through CO conversion
deeply depends on W/F. Since the catalyst slurry is
solely stirred by gas flow in the reactor, the range of
W/F is depends on the reactor dimensions and catalyst concentration.

Total CO conversion reached more than 95%

with the recycle ratio of 1.8. Since by-products of
this DME reaction were CO2 and small amount of
methanol, these by-products were easily removed from
unreacted syn-gas, so that high total CO conversion
was achieved.
(5) Product selectivity and DME quality
Table 5 shows typical product selectivity of 5TPD
pilot plant (CO2 was eliminated from the product selectivity calculation).
Table 5. Selectivity of 5TPD pilot plant
(Product C-mol ratio)

DME/(DME+Methanol)=0.91

(Product H-mol ratio) H2 O/(DME+Methanol+H2 O)=0.013

DME yield was as much as 90%. Very small

amount of H2 O was produced, which means that overall reaction well followed the DME synthesis reaction
(a). Table 6 shows typical product DME quality of
the plant. This quality was sufficient for IEAs recommended standards for DME as vehicle fuel, which
states that acceptable concentration of methanol is
lower than 0.01% and water is lower than 0.05%.
Figure 10. Effect of W/F on once-through CO conversion

Table 6. Product DME quality of 5 ton/day Plant

Product

content

DME

99.9%

Methanol + H2 O

< 0.01%

Figure 11 shows CO conversion as a function of

recycle ratio. Recycle ratio was a ratio of recycled
unreacted gas flow rate to make-up syn-gas flow rate.
While recycle ratio was changed, W/F was kept at
3.8, then once-through CO conversion was almost constant.

5. Engineering of the DME slurry reactor

Figure 11. Total CO conversion as a function of recycle ratio

(W/F=3.8 (gh)/mol, 260 , 5 MPa)

When the DME slurry reactor is scaled-up, both

catalyst activities and hydrodynamics of the catalyst slurry must be well considered. JFE started the
study of high pressure DME slurry reactor with a (9
cm-diameter2 meter-height) reactor and a (4 cmdiameter4 meter-height) reactor. Effects of reaction conditions and products yields were studied with
these reactors.
The size of the reactor of the 5TPD pilot plant was
0.55 meter-diameter15 meter-height. Axial slurry
mixing, gas-hold-up as well as the temperature controllability were tested with this reactor. The reactor
has 30% to 50% of gas-hold-up, which is very typical feature of a high-pressure slurry reactor. Liquid
(catalyst+oil) height itself was about 7 m, but slurry
height was about 10 to 14 m under operation conditions. Figure 12 shows stability and homogeneousness

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Takashi Ogawa et al./ Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

of the reactor inner temperature. In Figure 12, each

circle indicates temperatures of every 15 minutes at
each TI (Thermocouple) position for 8 h.
Since the temperature of the fed syn-gas to the
reactor was around 200220 , temperature of the
lower part of the reactor was slightly lower than 260
. As shown in Figure 12, most of reactor temperature in the slurry phase was even. The temperature
difference of the reactor higher than 1.8 m was almost
within 2 , which means that the slurry mixing was
very homogeneous. Also the sharp temperature drop
at the 10.1 meter TI position meant the slurry phase
did not form and had clear upper level.

Figure 13. Effect of gas residence time RTg on CO

conversion

6. Conclusions

Figure 12. Temperature stability of 5TPD DME reactor

DME yield deeply depends on W/F (Figure 9),

but gas residence time (RTg) in the slurry phase must
be considered because necessary time for reactants
phase transfer in the slurry phase is crucial in a large
reactor.
Figure 13 shows an effect of RTg on once-through
CO conversion. RTg was defined as the ratio of actual
fed gas flow rate to the slurry volume.

JFE direct DME synthesis technology successfully

finished 5TPD pilot plant project with achieving sufficient DME synthesis results and very stable DME
slurry reactor operation. Based on these results, DME
Development Co., Ltd is now conducting a 100TPD
DME demo-plant project in Hokkaido Japan in order
to establish commercial DME production technology.
This project is also supported by METI. The production of 100 tons of DME per day will start in 2004.
Acknowledgements
The authors would like to express sincere appreciation for Agency of Natural Resources and Energy,
Coal Division (METI) for their long term financial
support to the DME research Project.

RTg=[slurry volume]/[actual gas flow rate] (sec)

As shown in Figure 13, when RTg was more than
around 100 s, CO conversion reached almost constant.
This result means that the time for reactants transfer
in the slurry phase should be sufficient. The result
of Figure 13 also means that, as far as the reactor
diameter can be scaled-up, scale-up of the reactor is
scale-up of the reactor diameter because the reactor
does not need extra slurry height for excess RTg.

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